Volumes of activation for dissociative (D) mechanisms
|Title||Volumes of activation for dissociative (D) mechanisms: the substitution of pentacyanoferrate complexes by various nucleophiles|
|Author(s)||T. R. Sullivan, D. R. Stranks, J. Burgess, Robert I. Haines|
|Journal||Journal of the Chemical Society, Dalton Transactions|
|Abstract||The dissociative step of a dissociative, or D, substitution mechanism exhibits a volume of activation, V1, which is independent of the nature of the incoming nucleophile. For the reaction of [Fe(CN)5(3,5Me2-py)]3?(3,5Me2-py = 3,5-dimethylpyridine) with [CN]?, V1= 20.5 ? 0.8 cm3 mol?1; with pyrazine, V1= 21.2 ? 1.0 cm3 mol?1; and with imidazole, V1= 20.3 ? 1.0 cm3 mol?1. For the reaction of [Fe(CN)5(3CN-py)]3?(3CN-py = 3-cyano-pyridine) with [CN]?, V1= 20.6 ? 0.5 cm3 mol?1. These volumes of activation are shown to correspond to stretching of the Fe?N bond in the activated complex from 65 to 88% of the distance corresponding to complete dissociation of the leaving group from the [Fe(CN)5]3? moiety|
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